This invention is directed to improvements in room temperature polymerizable polyorganosiloxanes having very high viscosity (putty) and good dimensional stability upon curing or hardening. More particularly, this invention is directed to improvements in compositions that are generally of the type comprising two components, one component comprising organopolysiloxanes having vinyl groups, capable of undergoing addition reactions with organopolysiloxanes having silicone-bonded hydrogen atoms. The second component comprises a catalyst capable of promoting the addition of hydrogen atoms bonded to silicone atoms across the vinyl groups.
A major field for the use of certain of these room temperature curable polyorganosiloxane compositions is dentistry. Such materials are typically employed as impression materials for securing an analog representation of oral bard and soft tissue to support subsequent elaboration of crowns, bridges, dentures, an other oral prostheses. For dental use, extraordinary fidelity of structural reproduction is required in order to ensure good fidelity of oral prosthetic fit and the like. In this regard, changes in the dimensions of the impression material during curing are to be avoided. Moreover, the surface of the reproductions or oral prosthetics and the like must be exceptionally free from irregularities, blemishes, pits, and other imperfections. This is so because castings and prostheses derived from such impressions must have good surface qualities and be free from pits and irregularities in order to have proper fit, to achieve good adhesion, and to avoid irritation of sensitive mouth structures. These polyorganosiloxanes will also be useful in other fields where detailed reproductions are important such as in the science of metrology, laboratory processing of SEM and even jewelry fabrication and the like.
In employing polyorganosiloxanes as dental impression materials, a number of difficulties have arisen. First of all, tear strength tends to be low. It is necessary, in effectively taking an impression, to be able to easily remove the impression, from the dentition without tearing, particularly at thin marginal areas, to preserve fine detail. In the past, fillers of various types have been added to improve tear strength. Such additions may result in some improvement, on the order of about 10%, but such improvements have proved inadequate.
Paradiso in WO 93/17654 describes improving tear strength by incorporating multi-functional, including quadri-functional, polysiloxane components into the impression material, to add increased cross-linking to the resulting cured impression material matrix, particularly along the length of the linear vinyl end-stopped polysiloxane principal component. The Paradiso composition comprises SiOH groups capped off with Me3Si units that form pendants from the molecule. These pendants provide only mechanical or physical interlinking between the linear polysiloxane chains. This solution is deficient, being non-chemical and low in cross-linking density.
Voigt et al in EP 0 522 341 A1 describes very short processing times of 35-45 seconds for forming dentition bite registration devices, utilizing a xe2x80x9cQMxe2x80x9d resin as a means of speeding and increasing cross-linking. These resins comprise as Q, the quadri-functional SiO4/2 and as M, building blocks such as monofunctional units R3SiO1/2 wherein R is vinyl, methyl, ethyl or phenyl, or similar tri or bi-functional units. Voigt also notes that an elastomer with small elastic deformation having a higher tenacity and hardness results. However, hydrophobic poor wetting, such material lacks flexibility, having a low strain value, and is unsuitable for impression taking. The increased cross- linking rate of the QM resin also results in very limited processing times that are unsatisfactory.
The other major, well-known difficulties with polyorganosiloxane impression materials are caused by its inherent hydrophobic character. Such characteristics make reproduction of hard and soft oral tissue difficult since the oral cavity environment is wet and often contaminated with saliva or blood. The hydrophobicity of the impression material can result in loss of surface detail often at critical surfaces of the dentition.
A number of improvements of polyorganosiloxane impression materials focus upon adding a surfactant component to the dental impression material in order to reduce the hydrophobic nature of the polysiloxanes and make the composition more hydrophilic. Thus, Bryan et al in U.S. Pat. No. 4,657,959 describes adding an ethoxylated nonionic surface active agent containing siloxane or perfluoroalkyl solubilizing groups to achieve a three minute water contact angle below about 65xc2x0. While surfactants including hydrocarbyl groups, for rendering the surfactant soluble or dispersible in silicone prepolymer, are mentioned, including ethyleneoxy groups, the results achieved appeared to be less than optimal. Wetting but low tear strength.
In sum, polyorganosiloxane impression materials still need improvement in tear strength and wettability in order to provide improved use of these compositions for taking impressions of oral hard and soft tissues such that adequate working time, tear strength and wettability are provided. Also, sweating occurs as a result of the plasticizer that is in the composition migrating to the surface of the impression forming oily droplets of liquid. Sweating has been reported to cause melting of polystyrene impression trays and loss of impression detail.
Sweating as used herein refers to droplet formation of plasticizer formed on the outer surface of cured elastermeric impression material at 23xc2x0 C. within 24 hours of curing the cured material.
Non-sweating as used herein refers to elastomeric impression material which does not form visible droplets (and/or a film) of plasticizer on the outer surface- thereof at 23xc2x0 C. within 24 hours of curing the impression material.
Low liquid mass loss as used herein refers to elastomeric impression material which has less than 0.05 percent mass loss after 12 days at 23xc2x0 C. from the start of curing the impression material. A specimen is made of the putty using ADA 19 detail reproduction mold. The specimen is placed on top of an absorbent paper towel in a labeled crystallization dish and covered with a watch glass. 12 days after mixing the putty, the surface of the putty is observed, a record of the readability of the detail reproduction is made. The specimen is gently touched (blotted) with the paper towel to absorb any xe2x80x9csweatxe2x80x9d or oil from the surface. Then the specimen reweighed and the weight recorded. The results for the impression material of Example 1 and some commercially available dental impression materials are shown in the following Table I.
Non-sweating preferably refers to elastomeric impression material which after storage at 23xc2x0 C. for 24 hours has less than 10% by weight of the placticizer in the starting material separated from the stored impression material to form droplets (or a film) on the outer surface of the stored material. More preferably, there is less than 5% by weight of placticizer separated from material in accordance with the invention and most preferably, there is less than 1% by weight of placticizer separation from material in accordance with the invention.
Separation stable composition as used herein refers to a composition which is a single homogenous material after three weeks of storage in stationary position at 23xc2x0 C., and thus has not separated into two or more materials, so that such separation is visibly apparent. The lower density liquids do not migrate to the upper surface of a separation stable composition.
Consistency as used herein refers to consistency as measured by ADA specification number 19 revised Oct. 4, 1976 and is measured in mm.
Putty material in accordance with the invention is useful for making dentures, crowns, inlays and onlays and other prosthetics. The dentist takes an impression of the patient""s mouth by first applying a low viscosity material which is commonly dispensed from a syringe and then applying putty material in accordance with the invention over the low viscosity material. The putty material forces the low viscosity material into the minute details of the patient""s mouth for which an impression is being taken. The putty material hardens within about five minutes and then is readily removable by the dentist. The low viscosity material also hardens within about five minutes. Typically the low viscosity material forms a thin partial coating and the putty material forms a comprehensive layer surrounding a dentition for which an impression is being taken. Beneficially, the putty material in accordance with the invention is hydrophilic and captures minute details of the dentition.
A very high viscosity putty polyvinylsiloxane impression material useful to record hard and soft tissues in the mouth. The new impression material is a two component, hydrophilic non-sweating polymerizable organosiloxane separation stable material. The two component polymerizable organosiloxane composition, one component including a catalyst for polymerization, is for making a dental impression and comprises:
(a) a QM resin, containing vinyl groups;
(b) a linear vinyl terminated polydimethyl-siloxane fluid, forming with said QM resin a dispersion having a vinyl content of about 0.16 to 0.24 m-mole/g;
(c) a very high viscosity linear vinyl terminated polydimethylsiloxane having a molecular weight of 400,000-500,000, vinyl content 0.03 mmole/g;
(d) an organohydrogen polysiloxane for cross-linking said vinyl groups;
(e) an organoplatinum catalyst complex for accelerating polymerization of said components;
(f) an emulsifying plasticizer;
Placticize is normally an oily liquid. Placticizer typically is a low molecular weight nonpolymerizable compound, for example having a gram molecular weight less than 2000 and a viscosity less than 200 CPS.
(g) a retarder component in sufficient amount for temporarily delaying the onset of said polymerization;
(h) a filler; and
(i) a surfactant that imparts wettability to said composition, wherein said composition surface contact angle with water is less than 50xc2x0 after three minutes.
In accordance with a preferred embodiment of the invention, the placticizer is a emulsified by the surfactant. The mixture of placticizer and surfactant form a homogeneous phase within the putty composition in accordance with the invention.
Preferably, the dispersion of (a) and (b) has a viscosity of about 45,000-60,000 cps. The dispersion of (a), (b) and (c) may comprise a plurality of dispersion components having desired viscosities and QM resin contents. Preferably the QM resin-containing dispersions comprise a dispersion component having a viscosity of about 45,000-60,000 cps, the QM resin comprising about 20-25 weight % of the dispersion.
A preferred QM resin comprises a polyorganosiloxane comprising units of SiO4/2 an units of R1R22 SiO1/2 wherein R1 is unsaturated, preferably vinyl and R2 is alkyl, aryl, etc., such as methyl, ethyl, phenyl, etc. More preferably, the QM resin comprises the formula: 
The very high Viscosity linear vinyl terminated polydimethylsiloxane which imparts longer shelf stability, higher tear strength, reduced tackiness and improved tactile handling properties is preferably 5-15 percent by weight and most preferably 9-11 percent by weight of the composition.
The retarder component of the composition is a low molecular weight, vinyl functional fluid that is a linear or cyclic polysiloxane in an amount of at least about 0.010 weight percent of said composition. Preferably, the retarder component comprises: a fluid 1,3-divinyl, dimethyldisiloxane, in an amount of about 0.05 to 0.15 weight percent of said composition.
The composition includes a plasticizer that is capable of being emulsified to prevent xe2x80x9csweatingxe2x80x9d or migrating to the surface of the polymerized impression. The plasticizer is used to reduce tackiness of the composition during mixing of the base and catalyst components which are mixed by hand kneading. Preferably the plasticizer is comprised of an alkylphthalate, preferably at about 4-5 percent by weight of the base and catalyst compositions. Most preferably, the alkylphthalate is octyl benzyl phthalate.
The filler component of the invention comprises about 35 to about 55 weight percent of said composition and preferably includes a filler mixture of about 40 to about 50 weight percent.
A key component of the composition of the invention is the surfactant for imparting wettability, preferably comprising an HLB of about 8-11 and a pH of about 6-8. A most preferred surfactant is a nonionic surfactant, nonylphenoxy poly(ethyleneoxy) ethanol having an HLB of about 10.8. This surfactant also serves to emulsify the plasticizer and prevents its separation and xe2x80x9csweatingxe2x80x9d from the compositions.
After polymerization, the compositions of the invention include a tear strength of 300-400 psi and a contact angle with water of less than 50xc2x0 at three minutes.